Quaternary ammonium cyclic imides



fnited States Patent ()fii-ce U a v 3 133 (V2 I Tetrachlorophthalimidei r I v v QUATERNARY AMlllOlIIUM CYCLIC IMIDES I. Shibe, J12, River-ton, NJ., and Marcus Sitten- C1 '0 field, Philadelphia, Pa., assignors to Hollichem' Cor: V poration, Camden, N.J., a corporation of NewJersey" N N1) Drav ving.

Filed Jan. 16, 1962, SenNo. 166,699 3 Claims. v ((11. 260 -281) :QThis invention relates to quaternaryammonium compounds, and ,itparticularly relates to quaternary ammonium cyclic imides. n r

H Ithas heretofore been found that'the reaction products a V of various quaternary ammonium compounds and benzo sulfimide -(saccharin) were quite active biocidal agents,v

generally superior to ordinary quaternary ammonium compounds in'this respect and, furthermore, possessed f':a sweet,-pleasant taste not found in ordinary quaternaries' In addition, it was found that such quaternary I ammonium benzosulfimides' had inherent antistatic properties when incorporated in electrically non conductive materials suchas paper, glass, rubber, textiles, plastics and the like, and were also capable of being readily compleXed with halogens-to retain all the highlyefiective ger- 'micidal properties of the halogens While substantially V eliminatingtheir undesirable properties such as their rela- .tivelyhighdeigree of toxicity, their tendency to irritate PatenteclMay 12., 196d Benzothiazolinone:

6-methylbenzoxazo1inone:

S-methoxybnzothiazolinone i the skin and their tendency to'stain both skin' and fab O rics. It has" also been found that certain quaternary am- I v r V monium benzosulfimides have thixotropic properties mak- MeO i ng -thernhighly desirable thickening agents for various 7 NH purpqses; However, all 'these properties were heretofore n believed limited to the quaternary'ammonium benzosulf I S m de v I,""I t,hasfnovv been discovered thatthe above properties- For most Purposes the quaternary ammfmlum radlcal are n limited to tha quaternary ammonium bgnzosulfs may be selected from any of the well-known class of quat.

' imides but are, in addition, possessed in general by all other quaternary ammonium aromatic cyclic imides where thearomatic nucleus has attached thereto in those posi tions 'not attached to the cyclic imide radical a member of the group consisting of hydrogen, halogen, alkyl and alk- NHQOX wherein'X is agmemberzof'the' group consisting lllustrative of the aromatic I hthaliniiden cyclic imides utilizable in the present invention in addition to benzosulfimide are:

Naphthalimide:

2j,6 -'dichlorobenzoxazolinone:

' oiry, and wherein the cyclic imide radical has the formula ernary ammonium groups as, for example, the alkyl quaternaries such as lauryl trimethyl ammonium,-stearyl trimethyl ammonium, stearyl dimethyl ethyl ammonium, cetyl dimethyl ethyl ammonium, myristyl dimethyl ethyl ammonium lauryl dimethyl ethyl ammonium, tallow trimethyl ammonium, hydrogenated tallow trimethyl ammonium, coco trimethyl ammonium, di-hydrogenated 'tallow: dimethyl ammonium, 'di-coco dimethyl ammonium, disoya dimethyl ammonium, hydrogenated tallow; dimethyl ethyl ammonium, coco dimethyl ethyl ammonium,- tallow dimethyl ethyl ammonium and soya dimethyl'ethyl ammonium; the alkylaryl quaternaries such as lauryl die methyl benzyl ammonium, alkyl dimethyl benzylammo: nium, cetyl dimethyl benzyl ammonium, stearyl dimethyl benzyl ammonium, alkyl dimethyl dichlorabenzyl'ammo- Y nium, alkyl dimethyl ethylrbenzyl ammonium, alkyl dimethyl dimethyl benzyl ammonium, dodecyl benzyl trimethyl ammonium, dodecyl methyl benzyl trimethyl ammonium, octyl phenoXy ethdxy ethyl dimethyl benzyl ani'- monium, soya dirne thyl'benzyl ammonium, hydrogenated talloW dimethyl benzyl ammonium, tallow dimethyl benzyl alkenyl dichlorobenzyl hydroxyethyl imidazolinium, coco benzyl hydroxyethyl imidazolinium, coco. ethyl hydroxyethyl imidazolinium, stearyl ethyl hydroxyethyl imidazolinium, stearyl benzyl hydroxyethyl imidazolinium, stearyl dichlorobenzyl hydroxyethyl imidazolinium and stearyl ethyl benzyl hydroxyethyl imidazolinium; the mdrpho liniums such as coco methyl morpholinium and'myristyl ernary radical comprises four alkyl groups attached to i the nitrogen atom, one of these groups being a long chain group having at least 14 carbon atoms in the chain, preferably 14-22 carbon atoms, and the other three groups being lower alkyls having no more than carbon atoms in the chain. Among the quaternaries within this scope are myristyl trimethyl ammonium, cetyl trimethyl ammonium, stearyl trimethyl ammonium, arachidyl trimethyl ammonium, behenyl trimethyl ammonium, myristyl dimethyl ethyl ammonium, cetyl dimethyl ethyl ammonium, stearyl dimethyl ethyl ammonium, arachidyl dimethyl ethyl ammonium, behenyl dimethyl ethyl ammonium, and the like.

The various compounds embodying the present invention are generally prepared in substantially the same manner by reacting stoichiometric amounts of a selected quaternary, ammonium salt, such as a halide or sulfate, with a selected aromatic cyclic imide or with an alkali metal salt of such imide in an aqueous solution wherein the components react witheach other to form the desired product. Alternatively, an alcoholic solution may be used instead of the aqueous solution. Usually, agitation is required and the reaction may be carried out at ambient temperatures although, generally, the application of additional heat is preferable.

The following specific examples are provided for illustrative purposes only and with no intent to necessarily limit the inventive scope except as claimed.

Example 1 319.5 gms. of Arquad 16-50 (produced by the Armour Chemical Division, Armour & Co., Chicago, 111.), a product containing a 50% by weight concentration of cetyl trimethyl ammonium chloride, were diluted with 320 grams of deionized Water, thereby making a 25% solution of the chloride. tassium phthalimide were dissolved in 277 grams of deionized water. The two solutions were then blended and agitated for 5 minutes at ambient temperature and pressure to form a clear aqueous solution. This solution'was then evaporated to dryness in a forced draft oven at 212 F. The dry residue was extracted with hot 99% methanol. The alcoholic solution was then agitated and filtered and the insoluble salt removed. The filtrate was then evaporated to dryness. The residue was cetyl trimethyl ammonium phthalimide.

' Example 2 380 grams of a 50% aqueous solution of alkyl dimethyl benzyl ammonium chloride were diluted to 25 solids with 380 grams of deionized water. 98.5 grams mol) of naphthalimide were dissolved in 10 liters of deionized water containing 20 grams of sodium hydroxide. The two aqueous solutions were then mixed and heated, with agitation, to 100 C. An oily layer 92.5 grams /z mol) of po- 7 tetrachlorophthalimide.

4, The resulting solution was evaporated to 1 liter and cooled to room temperature, after which the salt sodium chloride was removed. The filtrate was then further evaporated to dryness. The residue, a dark brown, pasty solid, was cetyl pyridinium 2,6-dichlorobenzoxazolinone.

Example 4 224.25 grams /2 mol) of octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride were dissolved in 1 liter of deionized water. 161.5 grams of potassium tetrachlorophthalimide were dissolved in 5 liters of deionized water. The two aqueous solutions were then mixed and heated to 212 An oily layer was obtained and this oily layer-was separated in a separatory funnel and then dried in a vacuum oven. The resultant residue was octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium Example 5 68.5 grams /2 mol) of benzothiozolinone were dissolved in' 1 liter of isopropanol. 359 grams of a 50% solution of dodecyl benzyl trimethyl ammonium chloride were added with agitation; 20 grams of sodium hydroxide dissolved in'400 grams of ethyl alcohol were then added with agitation. The resultant solution was then evaporated to dryness in vacuum oven at 140 F. The resultant residue was then dissolved in 1 liter of 99% isopropanol. and was removed by filtration. The filtrate was then evaporated to dryness in a vacuum oven at 140 F. The final product obtained was a brown, pasty solid identified as dodecyl benzyl trimethyl ammonium benzothiozolinone.

Example 6 quinolinium 6 -methyl phthalimide.

Example 7 83.5 grams /z mol) of S-methoxy benzothiozolinone were dissolved in 1 liter of isopropanol. 192.75 grams (V2 11101 of cetyl dimethyl benzyl ammonium chloride were dissolved in 1 liter of deionized water. The alcoholic benzothiozolinone solution and the aqueous quaternary solution were then mixed and to the mixture was added 20 grams of sodium hydroxide. The resultant solution was evacuated to dryness in a vacuum oven at formed on the surface and was separated in a separatory I funnel. This oily layer was then dried in a vacuum oven at 140 F. to produce alkyl dimethyl benzyl ammonium naphthalimide as the end product.

Example 3 Example 8 19 2.75 grams of cetyl dimethyl benzyl ammonium chloride /2 mol) were diluted to 10% solids with deionized waiter and thissolution was then heated to F. at which point 28.5 grams of iodine crystals were added with agitation until the iodine was completely dissolved. The 10% quaternary ammonium iodine complex was then cooled to 75 F. 87.5 grams /2 mol) of potassium phthalimide was dissolved in deionizedwater to make a 10% aqueous solution and latter solution was then added to the quaternary solution with rapid and vigorous agitation. The resultant complex was separated as a crystalline mass and the supernatent water solution was decanted. The precipitate was then further washed with deionized Water. The cetyl dimethyl benzyl ammonium The resultant salt precipitated out Component:

7 of the present invention, bacteriosta-tic tests involving the following concentrations of representative compounds gave halos of at least agar plate studies:

, Staph.

Staphyloawn, coccus E. coli, E. antibi- Compound. aureus percent typhosi, otic-v 209, percent -resist-' percent "ant str., percent AlkyI dimethyl benzyl am-.. T- f wmonium benzosultlmide 0.01 0.1 0.1 0. 01

Alkyl dimethyl benzyl ammonium phthalimidennuc 0.01 0.1 0.1 0. 01 Alkyl dimethyl benzyl arn- 3 monium naphthylinnde 0. 01 0.1 0.1 0. 01 Alkyl dimethyl benzyl.am-. monium 2,6-dieh1oro-benz- Y oxazolinone 0. 01 ;1 0.1 0.01

Alkyl dimethyl benzyl arn-' monium tetrachlorophthal- 'imide; 0.01 0.1 0.1 0.01 Alkyl' dimethyl benzyl ammonium benzothiozolinone. 0. 01 0.1 0.1 0.01 Alkyl dimethyl benzyl ammonium" phthalimide-broe V mine (10% bromine) 0.006 0.06 0.006

groups attached to the nitrogen atom, wherein one alkyl 7 group is a long chain of at least 14 carbon atoms and the other three are lower alkyls of 1 to carbon atoms,

have Ivery effective thixotropic properties. These properties are retained :and may even be enhanced, in the presence of alkali metal, ammonium or alkaline earthsalts, For example, such compounds have been shown to retain their thixotropic propenties inraqueous solutions of 1 "I 10% sodium chloride, 10% calcium chloride and 5% sodium sulfate.

The following example of a white, indoor, water-base Parts by wt. Behenyl tnimethyl ammonium I phthalirnide (1.5% solution in H O) Tamol-73 1 (a sodium salt of a condensed .aryl

sulfonic acid; produced by Rohm & Haas Co,

Igepol 00-630 (100% nonyl phenoxy polyoxyethylene ethanol 7 produced by General Aniline and Film Corp., New York, N.Y.) 3

Water 2 50 Polyvinyl acetate (water emulsion having 50% solids) 345 ,TA.S.P.400 (a clay produced by Minerals &

Chemicals Corp. of ;America, Metuchen,

NJ.) r 75 The behenyl trimethyl ammonium phthalimide, the Tamol731,the Colloid 606, the ethylene glycol, the Titanox :RA-SO, the Snowflake, the A.S.P.400 and the Celite-281 are mixed until asmooth paste is formed. The water is then [added to achieve (the desired milling viscosity and the mass is passed through a suitable machine. The Carbitol, I-gepol CO-630 and polyvinyl acetate tare then-added and thoroughly mixed into the com-' position. If necessary, additional watermay be added to adjust the viscosity asdesired. I a

'I'he' thiXot-ropic properties of the above type compounds make them ideal thickening agents not only for. paints but for lotions, creams and ,the like. They are also eifective-ly used in the drilling of oil since they act to keep the clay in suspension and prevent itssettling out, thereby keeping the clayfluid andpreventingclogging. 'They also are elfective thickeners for pumping mixtures'whichare,

used to carry up the drilling refuse and' simultaneously act as biocides against algae and the like, thereby reducing the slime. They also act toautomatically seal up leaks and fissures in the substrata.

Quaternary ammonium aromatic cyclic of the type contemplated herein-are also very elfective antistatic agents when physically combined with electnically nonconductive substances such paper, textiles, skins,'leath- I ers, furs, plastics, etc. They may be incorporated in waxes and polishes for furniture, automobiles, floors, walls and thelike, These Waxes and polishes, when applied to the surfaces to be treated, prevent the accumulation of :dust, dirt, grime, etc. which would otherwise occur as the result of static electricity on such surfaces. Furthermore, these compounds are substantive to all of thetagforementioned; materials while their compatibility with poly- 1. A quaternary ammonium aromatic cyclic imidewherein the quaternary ammonium cation has the formula:

. v a [b 1114] wherein a and b are members of the group consisting of alkyl and cyclic constituents of pyridinium, isoquinoliniurn, picolinium, imidazolinium and morpholinium, c is i a member of the group consisting of alkyl," alkylaryl, aryl I and cyclic constituents of pyridinium, isoquinolinium and picolinium, 0, when itis a cyclic constituent-,being a member of the same ring as a and b, and d is a member of the group consisting of alkyl and alkylaryl, and wherein the aromatic cyclic imide anion isa member of, the group consisting of phthalimidenaphthalimide, benzoxazolinone and benzothiazolinone, the aromatic portion of said anion being substituted by a member of thegroup consisting of hydrogen, halide, lower alkyland lower alkoxy, there being a direct electro-valent linkage between the quater- I nary ammonium cation and the aromatic cyclic imide anion.'

2. 'A quaternary ammonium aromatic cyclic imidehalogen complex wherein the. quaternary ammonium aromatic cyclic imide consists of a quaternary ammonium cation having the formula:

wherein a and-b are members of the group consisting of alkyl and cyclic constituents of pyridinium, isoquinolinium, picolim'um, imidazolinium and morpholinium, c is a member of the group consisting of alkyl, alkylaryl, aryl wherein the aromatic cyclic imide anion is a member of the groupv consisting of phthalimide, naphthalimide, benzoxazolinone and benzothiazolinone, the aromatic portion of said anion being substituted by a member of the group consisting of hydrogen, halide, lower alkyl and lower alkoxy, there being a direct electro-valent linkage between the quaternary ammonium cation and the aromatic cyclicimide anion.

3. A quaternary ammonium aromatic cyclic imide wherein the quaternary ammonium cation has the formula:

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1. A QUATERNARY AMMONIUM AROMATIC CYCLIC IMIDE WHEREIN THE QUATERNARY AMMONIUM CATION HAS THE FORMULA: 